Carbonic carboxylic anhydrides

ABSTRACT

A process for esterification of cellulose wherein a cellulosic material is reacted under mild conditions and in the absence of a catalyst with mixed carbonic carboxylic anhydrides having the characteristic group WHEREBY A MONOVALENT OR DIVALENT CARBON ACYL GROUP IS BONDED TO THE CELLULOSE BY REPLACING ACTIVE HYDROGEN, WITH CONSEQUENT ESTER FORMATION, AND THERE IS RELEASED AS BY-PRODUCTS AN ALCOHOL OR GLYCOL AND CARBON DIOXIDE. In addition, novel compounds of the carbonic carboxylic anhydride class which are useful in the formation of cellulose esters according to the above-mentioned process, and which are characterized by the formula WHEREIN A&#39;&#39; is polyfluoroalkyl or polyfluoroalkoxyalkyl, R&#39;&#39;&#39;&#39; is a lower alkylene group, and G&#39;&#39; is selected from the group consisting of hydrogen and

United States Patent [191 Tesoro [54] CARBONIC CARBOXYLIC ANHYDRIDES[75] Inventor: Giuliaha Tesoro, Dobbs Ferry,

[73] Assignee: J. P. Stevens & Co., Inc., Garfield,

[22] Filed: June 18, 1970 21 Appl. No.: 57,887

Related US. Application Data I [62] Division of Ser. No. 653,632, July17, 1967, Pat. No.

[52] US. Cl ..-..260/408, 260/484 R, 260/413, 260/535 H, 260/463 [51]Int. Cl. ....C07c 69/00, C07c 53/28, C070 53/34 [58] Field of Search..260/463, 408

[56] References Cited UNITED STATESPATENTS 3,231,590 1/1966 l-lirano..260/404.5

Primary Examiner- Lewis Gotts Assistant ExaminerDiana G. RiversAltorney-Kenyon & Kenyon Reilly Carr & Chapin and J. Bradley Cohn 57ABSTRACT A process for esterification of cellulose wherein a cel- Feb.27, 1973 lulosic material is reacted under mild conditions and in theabsence of a catalyst with mixed carbonic carboxylic anhydrides havingthe characteristic group whereby a monovalent or divalent carbon acylgroup is bonded to the cellulose by replacing active hydrogen, withconsequent ester formation, and there is released as by-products analcohol or glycol and carbon dioxide.

wherein A is polyfluoroalkyl or polyfluoroalkoxyalkyl, R" is a loweralkylene group, and G is selected from the group consisting of hydrogenand 2 Claims, No Drawings CARBONIC CARBOXYLIC ANHYDRIDES Thisapplication is a division of application Ser. No. 653,632 filed July 17,1967 now US. Pat. No. 3,575,960.

The present invention relates to a process which modifies cellulose orother hydroxylcontaining polymers by replacing the active hydrogen atomsof the hydroxyl groups with a divalent or monovalent carbon acylradical. It relates as well to certain compounds useful in such process.

More particularly, the present invention relates to such a process asreferred to above wherein the hydroxyl-containing polymer is subjectedto esterification by one or more mixed carbonic carboxylic anhydrides.

The varied esters of cellulose are widely recognized to be valuablecompounds, especially in the manufacture of textiles and films. Priormethods for esterification of cellulose generally require reactionconditions which tend to damage the substrate material or to lead toundesirable by-products, such as acid. It is a primary object of thepresent invention, therefore, to provide a process for esterifyinghydroxylated polymers such as cellulose which can be carried out undermild conditions and without creation of undesirable by-products.

More particularly, it is an object of the present invention to provide aprocess for the esterification of an hydroxylated polymer which isefficient, and which will readily take place under relatively mild,neutral conditions, without a catalyst, and without formation of acidicby-products.

It is a further object of the present invention to provide a process foresterifying high molecular weight polyols which minimizesdepolymerization, degradation and hydrolytic cleavage as much aspossible.

It is another object of the present invention to provide a process forincreasing the wet and dry crease recovery properties of acellulosicfabric which has been esterified through a difunctionalcarbonic carboxylic anhydride.

Generally speaking, the present invention involves a process wherein ahigh molecular weight polyol, principally a cellulosic material, isesterified by treating it with a carbonic carboxylic anhydride compoundhaving the generic formula wherein R is an organic radical of from oneto about 20 carbon atoms selected from the group consisting of (l)monovalent radicals selected from the class consisting of alkyl,branched alkyl, alkenyl,

branched alkenyl, aralkyl, aryl, alkoxyalkyl and fluorinatedcounterparts of the foregoing monovalent radicals, and (2) the divalentradicals selected from the class consisting of alkylene, alkenylene,aralkenylene and arylene;

a is the integer 1 when R is selected as a monovalent radical and is theinteger 2 when R is selected as a divalent radical;

G is hydrogen when R is selected as a divalent radical, and is a memberselected from the group consisting of hydrogen and where A is an organicradical of from one to about 20 carbon atoms selected from the groupconsisting of alkyl, branched alkyl, alkenyl, branched alkenyl, aralkyl,aryl, alkoxyalkyl and fluorinated counterparts of the foregoingradicals, when R is selected as a monovalent radical;

R" is an alkylene radical of from one to about l2 carbon atoms, andthereafter subjecting the treated polyol to mild reaction conditionsuntil active hydrogen on said polyol is replaced by carbon acylradicals.

Necessarily the carbon acyl radicals which replace the active hydrogenin the cellulosic material may be either of the formula when R ismonovalent or of the formula when R is divalent.

In either case, it is seen that inasmuch as the carbon acyl radicals arebonded to the carbon backbone of the polymer through the oxygen atom ofthe hydroxyl group, the result is an esterification of the polymer.

The net effect of the process in generalized form is shown by thefollowing exemplary chemical equation, wherein an active site of anhydroxyl-containing polymer is denoted by HOPol, and the simplest typeof carbonic carboxylic anhydride is used (R' being lower alkyl andrepresenting R"G, when G is hydrogen).

From the simple equation (A) above it is seen that the by-products ofthe acylation or esterifying step are a lower alcohol and gaseous carbondioxide, both of which are nonmoxious are readily disposable.

Esters of cellulose have been widely used and studied and have assumedan importance in industry and commerce. In these compounds the selectionof the organic radical that enters the cellulose has been largely amatter of choice depending entirely upon the type of ester which isdesired. The present invention readily adapts itself to this broadselection of the organic radical R, thereby permitting an extensiverange of desired products. Consequently, equation (A) above is merelyrepresentative of reactions according to the present invention, and morecomplex carbonic carboxylic anhydrides within the generic formula may beused to esterify the hydroxyl-containing polymer in like,

manner. For purposes of clarity and for isolation of particularly uniquefeatures associated with the use of certain of the carbonic carboxylicanhydrides in the present invention the class of such compoundsrepresented by the generic formula given above may be broken down intothree sub-generic groups, which are hereinafter designated Series I, IIand III as follows:

Series I (R is monovalent, a is l, G is H, and R"H is abbreviated belowas R, a lower alkyl):

Series ll (R is monovalent, a is l, G is i ii (l i ll (II) Series III (Ris divalent, a is 2, G is H, and R", a lower alkyl, stands for R"l-l):

(III) Many of the carbonic carboxylic anhydrides used in the process ofthis invention are obtainable by known methods. Generally they can beprepared by a condensation reaction between a carboxylic acid and asuitable chloroformate, the by-product hydrogen chloride immediatelybeing neutralized in situ by an acid acceptor. As used herein and in theclaims, the general terms carboxylic acid and alkyl chloroformate areunderstood to include dicarboxylic acids and alkylenebis(chloroformates), respectively. Methods of preparation of carboniccarboxylic anhydrides of Series I, ii and III are exemplified by thefollowing Reactions B, C and D, respectively.

0 Mono- Alkyl (I) carboxylic chlorofonnate acid RCO-H C1COROCC1 HOC 2HCl H 0 A (i ll Alkylene bls(ehloroformate) RCOCOROC-OC R llllli (II) (C)R C0H 2Cl-COR R CO-COR II N 2HC1 H 0 2 O O O 1 Dicarboxylic Alkyl III 1)acid ehloroformate Considering the foregoing reactions, it is apparentthat any of several series of carbonic carboxylic anhydrides may be usedin the process of this invention, e.g.,

Series I from a monocarboxylic acid and an alkyl chloroformate,

Series ll from a bis(chloroformate) and 2 molar parts of amonocarboxylic acid, and

Series ill from a dicarboxylic acid and 2 molar parts of an alkylchloroformate.

in the Table l, 2 and 3 below there are shown the fonnulas and names ofseveral typical carbonic carboxylic anhydrides which are useful in thepresent invention, and which for convenience sake have been divided intothe classificationsof Series i, ll and Ill, respectively:

TABLE 1 Series I: rap-0% OR, where R is ethyl Name of Anhydride CH,Acetic Ethylcarbonic CH,=CH Acrylic Ethylcarbonic C H,, EthylcarbonicLauric C,,H Ethylcarbonic Stearic C l-l Benzoic Ethylcarbonic (3H3 CaH1CEthylcarbonic Neoheptanoic CH; CHIML- Ethylcarbonic Neotridecanoic Cll';

heptyloxy )propionic] Divalent R Name of Anhydride -(CH,)6- Suberic Bis(ethylcarbonic) -(-CH )4- Adipic Bis (ethylcarbonic) --(CH,)8- SebacicBis (ethylcarbonic) Although many of the above compounds are old in theart and their methods of preparation are well known to those skilled inthe art, certain of such compounds, especially in Series I and II, arein themselves novel and form a part of the present invention. Thesenovel carbonic carboxylic anhydride'compounds may be defined by thefollowing generic formula:

wherein A is selected from the group consisting of polyfluoroalkyl and.polyfluoroalkoxyalkyl, R" is a lower alkylene of up to 20 carbon atoms,and G is selected from the group consisting of hydrogen and acids, asdefined above, can be prepared, isolated, and

effectively used for the esterification of polyhydroxylated polymers.

In general, the carbonic carboxylic anhydrides having fluorinated groupsmay be prepared by the condensation reaction of a polyfluoroalkanoicacid with a diol bis(chloroformate) or alkyl chloroformate. One or moreof the ingredients is usually diluted in a solvent,

such as ethyl ether, and thereafter reacted in the presence of a weakbase, such as triethylamine. The reaction proceeds below roomtemperature and it is preferably maintained at about 0 C. or below.Further particulars will be evident'by reference to the examples. v

The esters which have been created by the use of the novel polyfluorocompounds defined above can be useful in the preparation of textiles ofimproved stain resistance and water repellency.

When practicing the process of the present invention it is generallypreferred that an anhydride be selected that is relatively high-boiling.For example, in esterifying a cellulosic fabric with a carboniccarboxylic anhydride, a relatively simple technique of a one-steppad-cure may be used if the anhydride is relatively high-boiling.Esterification agents which meet this criteria and which areparticularly suited to this technique are those which have been preparedfrom a compound that has two chloroformyloxy groups, e.g.,

Ethylene glycol bis(chloroformate), i.e., R" is CH CH is representativeof such a starting material. It has been found that such a compound canbe used, for example, to prepare all of the individual esterifyingagents listed in Table 2. The resulting agents are all high-boiling andsuited to the simple pad-cure treatment which may be used according tothe invention. The method of using a diol bis(chloroformate) as a meansfor preparing high-boiling esterification agents which are particularlysuited to the purposes of the present invention constitutes part of thepresent invention, and Examples 1-5 and 10 are exemplary of it.

Most-of the compounds of Series II and III are relatively high-boiling,including all of those set forth in Tables 2 and 3; however, certaincompounds within the generic formula may be relatively low-boiling,especially those in the sub-genus Series I. If it is found by experiencethat the particular compound being used is not sufficiently high-boilingto be readily applied by pad-cure techniques, then a wet reaction orimmersion technique can be used on cellulosic substrate. The use of suchtechniques is also set forth in the examples, e.g., Example 11.

Particularly effective results are achieved when a hydroxyl-containingpolymer is treated by a carbonic carboxylic anhydride, such as thosedefined by the subgene'ric Series III, which is capable of formingcrosslinks with the polymer. The reaction as it applies to cellulose,for example, can be represented as follows:

The net effect is that cellulose is cross-linked by esterification witha dicarboxylic acid, such as suberic acid, adipic acid or sebacic acid.The application of this principle is that it provides an improved meansfor imparting crease recovery (both wet crease recovery and dry creaserecovery) to cellulosic fabrics. Because no acidic catalyst is required,and because the reaction is effected under relatively mild, neutralconditions, this process permits cellulosic fabric to be modified fordurable creases and pleats without significant weakening of the strengthof the textile. The efficiency of the cellulose reaction with thecarbonic carboxylic anhydrides prepared from dibasic acids is quitehigh, and in most cases approaches 100 percent.

Similarly, carbonic carboxylic anhydrides that have a residual vinylgroup after reaction with the cellulose may undergo further addition orcross-linking through the vinyl group. For example, acrylicethylcarbonic anhydride (See Table 1) has an active vinyl group, and isuseful for making acrylic esters of hydroxyl-containing polymers. Suchesters can be cross-linked through addition polymerization, as thefollowing equation (where n represents the degree of polymerization).

| Cell Although one of the outstanding advantages of the presentinvention is that mild conditions may be used which will not degradatethe substrate or polymer structure, the esterification reaction itselfmay be carried out over a very wide range of conditions.

Thus, the esterification may take from a few minutes to several hours,depending upon the other conditions chosen, particularly temperature.High temperatures require less time within which to effectesterification, and vice versa. In general, however, a suitable reactionmay be obtained by using temperatures in the range of about C. to 200 C.or even higher, and by using times in the range of about 24 hours to 5minutes or less. Obviously the permissible range of reaction conditionsis quite extensive, and the optimum conditions for any particularreaction involving a selected polymeric substrate and a selectedcarbonic carboxylic anhydride can be arrived at quickly in an empiricalmanner.

The carbonic carboxylic anhydride is preferably used while diluted in anappropriate solvent. Suitable solvents are those which are polar andhence swell the cellulosic substrate. A preferred polar solvent is N,N-dimethylformamide. Other suitable illustrative solvents areN,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, l,S-dimethyl-l-2-pyrrolidinone, dimethyl sulfoxide and tetramethylenesulfone.

Having thus described the general process, hereinbelow are set forthseveral specific examples further illustrating the use of the process ofthe present invention and the advantages that can be derived from it.Examples l-lO describe methods by which one may prepare novel carboniccarboxylic anhydrides which are useful in the present invention, andExamples 11-28 describe specific embodiments of the process andcompounds of the present invention.

EXAMPLE 1 Preparation of Ethylenebis [carbonic 3-( lH,ll-l,7H-Dodecafluoroheptyloxy) Propionic Anhydride] 3-( l H, lH,7H-Dodecafluoroheptyloxy)propionic acid (40.4 grams, 0.1 mole) wasdissolved in 200 ml. of ethyl ether. The solution was cooled at 0 C. andtriethylamine (10.1 grams, 0.1 mole) was added. At 0 C. ethylene glycolbis(chloroformate) (9.35 grams, 0.05 mole) was added in 15 minutes withstirring. Upon completion of the addition, the mixture was stirred foranother 30 minutes and allowed to warm to room temperature. The mixturewas filtered to remove triethylammonium chloride, and the filtrate waswashed with 50 m1. of a saturated solution of sodium bicarbonate, thenby 50 ml. of water, and finally dried with sodium sulfate. Ethyl etherwas distilled off in vacuo at 30 C. leaving 39 grams (an percent yield)of ethylenebis[carbonic 3-(1H,1H,7l-ldodecafluoroheptyloxy)propionicanhydride].

EXAMPLE 2 Preparation of Ethylenebis '(carbonic[Bis(trifl uoromethyl)methoxylAcetic Anhydride) EXAMPLE 3 Preparation of Ethylenebis(carbonic[Fluorobis( trifluoro-methyl)methoxy1Acetic Anhydride)[Fluorobis(trifluoromethyl)methoxy]acetic acid (122 grams, 0.5 mole),ethylene glycol bis(chloroformate) (46.75 grams, 0.25 mole), andtriethylamine (50.5 grams, 0.5 mole) were allowed to react, theprocedure being similar to that of Example 1. The yield of ethylenebis[carbonic[fluorobis(trifluoromethyl)- methoxylacetic anhydride] was 129grams (86%).

EXAMPLE 4 Preparation of Ethylenebis (carbonic Acrylic Anhydride)Acrylic acid, ethylene glycol bis( chloroformate) and triethylamine inthe molar proportion of 2, 1 and 2 were allowed to react, the procedurebeing similar to that of Example 1. The yield of ethylenebis(carbonicacrylic anhydride) was 40 percent of the theoretical amount.

EXAMPLE 5 Preparation of Ethylenebis (carbonic Neoheptanoic Anhydride)(3112 --00 H CICOCH 2cm I z I: H 2 1 2HC3 CIIII O 2 Neoheptanoic acid,ethylene glycol bis(chloroformate), and triethanolamine in the molarproportion of 2, l and 2 were allowed to react, the procedure beingsimilar to that of Example 1. The yield of ethylenebis(carbonicneoheptanoic anhydride) was 86%.

EXAMPLE 6 Preparation of Ethylcarbonic Neoheptanoic Anhydride -HCl 0 0Cali! CzH fi h J)2 0 0 CaH7 Neoheptanoic acid, ethyl chloroformate, and

triethanolamine in equimolar proportion were allowed to react, theprocedure otherwise being similar to that of Example 1. The yield ofethylcarbonic neoheptanoic anhydride was 90%.

EXAMPLE 7 of Example 1. The yield of ethylcarbonic neotridecanoicanhydride was 78 percent.

EXAMPLE 8 Preparation of Ethylcarbonic (Polystyrene)carboxylic AnhydrideFirst, (polystyrene)carboxylic acid was prepared by the following seriesof reactions in which the degree of polymerization is denoted by n, andBu stands for CH CH CHCH it) CH=CH2 Bl1[ n BuLl CsHs CHCII2 Ll CO2 05115LiCl CeHs n bled into the mixture during a period of 1 hour. By-

product lithium chloride was filtered off. The filtrate was concentratedconsiderably by evaporation. The desired product was precipitated by theaddition of methanol at "20 C., collected on a filter, and dried. Theyield of carboxyl-terminated polystyrene was grams. The equivalentweight of (polystyrene)carboxylic acid was found to be I810 by titrationwith standard base. Hence, the average degree of polymerization, n, wasbetween 16 and 17.

Next, the carboxyl-terminated polystyrene was converted to ethylcarbonic(polystyrene)carboxylic anhydride in accordance with the followingreaction.

. 0 Bu CHCH2 00211 0193002115 021mm 10115 n i loi loCzHs 11 Thecarboxyl-terminated polystyrene (90.5 grams, 0.05 mole) and 5.05 grams(0.05 mole) of triethylamine were dissolved in 1 liter of ethyl ether.The solution was cooled to 0 C. To it was added 5.43 grams (0.05 mole)of ethyl chloroformate dropwise in 15 minutes, while the reactiontemperature was kept at 0 C. The reaction solution was allowed to standfor 2 hours and warm to room temperature. Triethylammonium chloride wasfiltered off. The filtrate was evaporated to dryness, resulting in ayield of 87 grams of ethylcarbonic (polystyrene )carboxylic anhydride.

EXAMPLE 9 Preparation of Ethylcarbonic 1 l-(fluorobis(trifluoromethyl)-methoxy]undecanoic Anhydride First, 1l-[fluorobis(trifluoromethyl )methoxy 1 undecanoic acid was prepared bythe following reaction.

NaOH

H01 aC)zGO(CH;)mCOzH Acidification 1|? During a 30 minute period, atotal of 260 grams (1.56 moles) of hexafluoroacetone was bubbled into amixture of 239 grams (1.56 moles) of cesium fluoride in 700 ml. of drybis-(2-methoxyethyl) ether at -40 C. Then the mixture was allowed towarm to room temperature, and methyl 1 l-bromoundecanoate (340 grams,0.90 mole) was added promptly. The mixture was stirred at 75 C. for 48hours. Next, the solid matter (mainly cesium bromide) was filtered off.The filtrate was washed by two separate 2-liter portions of water. Ethylether was added to the organic layer, which was dried over anhydrousmagnesium sulfate. After removal of ethyl ether by distillation, methyl1 l- [fluorobis-(trifluoromethyl)methoxy]undecanoate (300 grams) wascollected mainly at 80 to 85 C. during distillation at approximately 0.1torr. Saponification was effected by allowing the following mixture toremain for 2 hours at room temperature: 285 grams (0.74 mole) of theester in 1 liter of ethanol (denatured by 5 percent of its volume ofmethanol), and 60 grams (1.5 moles) of sodium hydroxide dissolved in 60ml. of water. Then the mixture was poured into 2 liters of water, andacidified with concentrated hydrochloric acid to pH 3. The oily layerwas separated, dissolved in ethyl ether, and washed with water untilpractically neutral. The organic solution was dried over anhydrousmagnesium sulfate. The solvent was volatilized off, leaving 279 grams of1 l-[fluorobis(trifluoromet hyl)methoxy]undecanoic acid.

Next, the heptafluoro ether-acid was converted to ethylcarbonic 1l-[fiuorobis( trifluoromethyl)methoxy] undecanoic anhydride by means ofthe following reacnon.

( aC)zC0-(CH2)1oCOzH ClCOCzI-h (0.1mm

(CzHs)aNHCl s )2Cl1-O(CH2)1ofi3OFOCzH F A solution consisting of 219grams (0.59 mole) of the heptafluoro ether-acid and 59.7 grams (0.59mole) of triethylamine in 1 liter of ethyl ether was cooled to 0 C.During a minute period a total of 64.3 grams (0.59 mole) of ethylchloroformate was added dropwise at 0 C. Then the mixture was stirredfor 1 hour and was allowed to warm to room temperature. Triethylammoniumchloride was filtered off. The filtrate was washed with a saturatedsolution of sodium bicarbonate, next with water, and then dried overanhydrous sodium sulfate. After the solvent had been evaporated, theresulting yield of ethylcarbonic l1-[fluorobis-(trifluoromethyl)methoxy]undecanoic anhydride was 234 grams.

EXAMPLE 10 Preparation of Ethylenebis [carbonic 4-[Fluorobis(tri-fluoromethyl)methoxy] butyric Anhydride First,4-[fluorobis(trifluoromethyl)methoxylbutyric acid was prepared by thefollowing reaction.

A total of 350 grams (2.1 moles) of hexafluoroacetone was bubbled into amixture of 123 grams (2.1 moles) of potassium fluoride in 800 ml. of drybis( 2-methoxyethyl) ether at 40 C. Then the mixture was allowed to warmto room temperature and methyl 4-bromobutyrate (380 grams, 2.1 moles)was added promptly. The mixture was stirred at C. for 16 hours. Afterthat, it was poured into 2 liters of water. The organic layer wasdissolved in ethyl ether and dried over anhydrous magnesium sulfate.After removal of ethyl ether by distillation, methyl 4-[fluorobis-(trifluoromethy1)methoxy]256 grams) was collected mainly at C. duringdistillation at approximately 10 torrs. Saponification was effected bystirring the following mixture for 1.5 hours at room temperature: 256grams (0.895 mole) of the ester in 2 liters of methanol, and 72 grams(1.8 moles) of sodium hydroxide dissolved in 72 grams of water. Then themixture was poured into 4 liters of water, and acidified withconcentrated hydrochloric acid to pH 3. The oily product was dissolvedin ethyl ether, and washed with water until practically neutral. Theorganic solution was dried over anhydrous magnesium sulfate. The solventwas volatilized off, and a total of 195 grams (0.717 mole) of4-[fluorobis(trifluoromethyl)methoxy1butyric acid was collected at C.during distillation at 2 torrs.

Next, the heptafluoro ether-acid was converted to ethylenebis[carbonic4-[fluorobis(trifluoromet hyl)methoxy]butyric anhydride] by means of thefollowing reaction.

A solution consisting of grams (0.68 mole) of the heptafluoro ether-acidand 68.7 grams (0.68 mole) of triethylamine in 1.5 liters of ethyl etherwas cooled to 0 C. During a 15 minute period a total of 65.5 grams (0.35mole) of ethylene glycol bis(chloroformate) was added dropwise at 0 C.Then the mixture was stirred for 1 hour and was allowed to warm to roomtemperature. Triethylammonium chloride was filtered off. The filtratewas washed with a saturated solution of sodium bicarbonate, next withwater, and then dried over anhydrous sodium sulfate. After the solventhad been evaporated, the resulting yield of ethylene-bis[carbonic4-[fluorobis(trifluoromethyl)methoxy]butyric anhydride] was 200 grams.

Having thus set forth exemplary procedures for the preparation ofcarbonic carboxylic anhydrides, there is shown in the examples below howsuch carbonic carboxylic anhydride compounds, as well as others, can beused according to the invention to esterify cellulosic materials.

The tests which are used in the examples to show the relative physicalchanges which have occurred by reason of the esterification reactions,and the units and legends used therein, are as follows:

Crease Recovery angle, in degrees, total of readings in filling (F) andwarp (W); Monsanto Method, ASTM D-l295-60T.

Stiffness (Cantilever), in milligrams per centimeter; ASTM D-l388-55T.

Tear Strength, in pounds in warp (W) direction, Elmendorf Method, ASTMD-l424-59.

Tensile Strength, in pounds in warp (W) direction, ravel 1 inch stripmethod; Federal Specifications for Textile Test Methods, CCC-T-19l6,Method 5104.1.

The conditioning of samples for testing purposes was at 21 ilC. and arelative humidity of 65 12%. in the tables presenting data all parts andpercentages are by weight unless otherwise noted.

The following legends have been used;

OWB: On the weight of the bath used for padding, in

per cent.

OWF: On the weight of the fiber (or fabric), i.e., the percentage basedon the weight of the fabric prior to padding. OWB times WPU/100% OWF.

WPU: Wet pickup, i.e., the percentage of wet add-on OWF, measureddirectly after padding.

Moisture Regain (in is the weight of moisture calculated as a percentageof the bone-dry weight, ASTM D-629-59T.

Extent of Utilization of Padded Reagent is the efficiency of reaction,calculated as f (100%) E/(% OWF) c where f is the found or observedweight gain, e is the equivalent weight of the residue of atomsacylating the cellulose, E is the equivalent weight of the carboniccarboxylic anhydride, and OWF is defined EXAMPLE 12 A sample of 80 X 80cotton print cloth was conditioned and weighed as in Example 1 1. Thenit was padded with a 20 percent solution of acrylic ethylcarbonicanhydride in dimethylformamide. Rollers on the laboratory padder wereset so the resulting wet pick-up was 92 percent. Without drying, thesample was placed in a test tube, which was sealed and kept for 4 hoursin a water bath at 90 C. After the treatment, the sample was rinsed,conditioned and weighed as those steps were carried out in Example 11.The weight gain, corrected for moisture regain, was 1.7 percent,indicative that 24 percent of the amount of reagent padded on the fabrichad under-gone chemical reaction to form an acrylic ester of cellulose.

EXAMPLE 13 as above. ric) cellulose are shown in Table 4.

TABLE 4 Ethylcarbonie lauric anhydride, Extent Crease percent, fromCorrected utilization recovery, dimethylformamide weight of paddeddegrees Tensile Tear Conditions for gain, reagent, strength, strengthSample OWB WPU OWF esterification percent percent Dry lbs. bs

20 84 16. 8 4 hrs. at 90 C 1.1 9 20 90 18. 0.25 hr. at 135 C- 6. 9 58226 196 52 1. 6 20 88 17. 6 0.5 hr. at 135 O 7.2 66 214 205 56 1.Untreated 193 162 59 1 7 1 Average results on 5 specimens.

EXAMPLE 11 The following reaction was carried out to make an acetylatedcellulose: Cel10-H HzCffi-0 -0O1Ht O CellO-gllCHa 002 11-00211,

Two samples of plain weave cotton fabric, commonly known as 80 X 80print cloth, were conditioned and weighed on an analytical balance. Thesamples were immersed in a percent solution of acetic ethylcarbonicanhydride in N,N-dimethylformamide for 2 hours (Sample 10a) and 6 hours(Sample 11b), respectively. The temperature of the liquid was maintainedat 90 C. in each instance. Upon removal from the solution, each samplewas rinsed thoroughly in dimethylformamide and then in water containing0.1 percent of a nonionic detergent (isooctylphenol bound to an averageof 9 or 10 repeating units of polymerized ethylene oxide). After havingbeen dried, the samples were conditioned and weighed. Weight gains for11a and 11b resulting from acetylation were, respectively, 5.3 and 6.1percent, corrected for moisture regain. In the warp direction, tensilestrengths were respectively 58 and 54 pounds. The tensile strength ofuntreated 80 X 80 print cloth was 59 pounds in the warp direction,consequently there was no substantial loss in strength associated withthe esterification.

Greater yields were obtained for the treatments at 135 C. than for thatat 90 C. Despite the fact that the extents of the utilization of thereagent padded on the fabric were appreciable (58 and 66 percent),mechanical strength values were not greatly impaired as compared withthe untreated control specimens. On the other hand, crease recovery wassignificantly improved in comparison with the untreated (control)specimens.

' EXAMPLE 14 Three samples of X 80 cotton print cloth, 14a, 14b and 140,were conditioned and weighed as in Example I 1. Then they were paddedwith a 20 percent solution of ethylcarbonic stearic anhydride indimethylformamide in accordance with percentages shown in the followingTable 5. Sample 14a was kept wet in a sealed test tube at C. for 4 hors. The other samples were cured at C. for various times as indicated inTable 5. After the various heat treatments, each sample was rinsed,conditioned and weighed as those steps were described in Example 1 1.The treatments formed stearic esters of cellulose, and the remainingpertinent data, including the results of evaluation of performance, areshown inTable 5.

It is seen that the esterified cellulose showed significantly improvedcrease recovery with no significant loss in tear strength. Moreover, theesterified cellulose was characterized by a softer hand, as may be seenby the reduced stiffness.

TABLE Ethylcarhonic stearie anhydride, Extent Crease percent, fromCorrected utilization recovery, dimethylformamide weight of paddeddegrees Tear Conditions for gain, reagent, strength, Stiffness SampleOWB WPU OWF esterilication percent percent Dry Wet lbs. mg./cm

20 73 14. 6 4 hrs. at 00 C 1.1 10 20 72 14. 4 0.25 hr. at 135 C.. 7. 475 228 196 1. J 75 20 72 14. 4 0.5 hr. at135 C..." 7. 4 75 214 205 l. 475 Untreated 193 162 1. 7 105 1 Average results on 5 specimens.

EXAMPLE 16b and 160 were were cured at 121 C. and 135 C. for

Three samples of 80 x 80 cotton print cloth, 15a, 15b and 150, wereconditioned and weighed as in Example 1 1. Then they were padded with a20 percent solution of benzoic ethylcarbonic anhydride indimethylformamide in accordance with percentages shown in the followingTable 6. Sample 150 was kept wet in a sealed test tube at 90 C. for 4hours. The other samples were 15 minutes, as indicated. Sample 16d wasimmersed in a percent solution of ethylcarbonic neoheptanoic anhydridein dimethylformamide for 4 hours at 90 C. After the various heattreatments, each sample was rinsed, conditioned, and weighed as thosesteps were described in Example 11. Extents of esterification to formneopeptanoic esters of the cellulose are shown in Table 7.

cured at 135 C. for various times as indicated in Table 6. After thevarious heat treatments, each sample was rinsed, conditioned and weighedas those steps were described in Example 11.

The process resulted in the formation of benzoic esters of cellulose,the extent of esterification being somewhat higher for the samplestreated at 135 C.

Three samples of 80 X 80 cotton print cloth, 17a, 17b and 170, wereconditioned and weighed as in Example 11. Two of them (17a and 17b) werepadded with a 20 percent solution of ethylcarbonic neotridecanoicanhydride (the product of Example 7) in dimethylformamide in accordancewith data tabu- TABLE 6 bcnzolc ethylcarbonie anhydride, Extent percent,from Corrected utilization dimethylformamide weight of padded Conditionsfor gain, reagent, Sample OWB WPU OWF esterifieatlon percent percent 2088 17. 6 4 hrs. at 90 C 2. 6 28 20 94 18. 8 0.25 hr. at 135 5. 8 57 2088 17. 6 0.5 hr. at 135 C 5. 7 61 EXAMPLE l6 lated below in Table 8.Sample 17a was kept wet in a sealed test tube at 90 C. for 4 hours.Sample 17b was Four samples of 80 X 80 cotton print cloth, 16a, 16b, 16cand 16d, were conditioned and weighed as in Example 11. Three of them,16a, 16b, 16c, were padded with a solution of ethyl-carbonicneoheptanoic anhydride (the product of Example 6) in dimethylfonnamideand treated and tested in accordance with the data tabulated below inTable 7. Sample 16a was kept wet in a sealed test tube at 90 C. for 4hours. Samples cured for 0.25 hour at 135 C. Sample 17c was immersed ina 25 percent solution of ethylcarbonic neotridecanoic anhydride indimethylformamide for 4 hours at 90 C. After the heat treatment, eachsample was rinsed, conditioned and weighed as those steps were describedin Example 11. The treatment resulted in formation of neotridecanoicesters of cellulose. Results are given in Table 8 below.

TABLE 8 Ethylearbonic neotrideeanoic anhydride, Extent percent inCorrected utilization dimethylformamide weight of padded Conditions forgain, reagent, Sample OWB WPU OWF esterification percent percent 17a 2067 13. 4 4 hrs. at 90 C 1. 6 14 17b 20 13.0 0.25 hr. at 135 C 1.7 18 17c25 4 hrs. at C 1.6

1 Not padded; immersed.

EXAMPLE 18 Three samples of 80 X 80 cotton print cloth, 18a, 18b

and 18c, were conditioned and weighed as in Example 1 1. Two of them(180 and 18b) were padded with a 25 Example 2, in dimethylformamide,andcured, all in accordance with data tabulated below in Table 11. Thethird sample (200) was immersed in a 20 percent solution of the sameanhydride in dimethylformamide for 4 percent solution of ethylenebis(carbonic acrylic an- 5 hours at 90 a :::::22:: hydride), the product ofExample 4, in dimethylformai e i g9 l l U Th 3 It tab mide as set forthbelow in Table 9. Samples 18a and i g 3, gi zgizz s 18b were cured at135 C. for various times as int f st rs ofceuulose y dicated. Sample 18cwas immersed in a 20 percent 6 xy ace Ce 6 solution of ethylenebis(carbonic acrylic anhydride) in TABLE 1 1 dimethylformamide for 4 hoursat 90 C. After the heat treatment, each sample was rinsed, conditionedand Anhydride of corrected Example 2,%, in Conditions for Wei ht weighedas those steps were described in Example 1 l. sample rpimethylfgrmamideEs'erification t- The treatment resulted in the formation of acrylic l5OWB wPU OWF esters of cellulose. Ph sical testin of th d 95 y g ded i b20 90 13.0 0.5 hr. at 135C. 0.58 ples showed improved crease recoverywith but slight 20c 20 Not padded; 4hrs. at90 C. 0.39 loss in tensilestrength. Immersed) TABLE i;

Ethylenebis (carbonic acrylic anhydride), Extent Crease percent, inCorrected utilization recovery, Tensile dimethylformarnide weight ofpadded degrees strength, Conditions for gain, reagent, lbs. Sample OWBWPU OWF esterification percent percent Wet Dry 18a 83 20.7 0.25 hr. at135 c 4.0 46 230 232 41 18b 25 82 20.5 0.5 hr. at 135 4.4 51 233 225 4418c 20 4m. at 90 0 2.6

1 N 0t padded; immersed.

EXAMPLE 19 3O EXAMPLE 21 Four samples of 80 X 80 cotton print cloth, 2la, 21b, 21c and 21d, were conditioned and weighed as in Example ll.Three of them (21a, 21b, 21c) were padded with a 20 percent solution ofethylenebis[carbonic 3- 1H, 1 H,7H-dodecafluoroheptyloxy)propionicanhydride], the product of Example 1, in dimcthylformamide, and cured inaccordance with data tabulated below in Table 12. The fourth sample(21d) was immersed in a 20 percent solution of the same anhydride indimethylformamide for 4 hours at 90 C. After the esterificationreaction, each sample was rinsed, conditioned and weighed as in Example11. The results tabu- TABLE 16 Ethylenebis (carbonic neoheptanoic anhy-Extent Crease dride) ,percent, in Corrected utilization recovery,

dimethyllormamide weight padded degrees Tensile Conditions for gain,reagent, strength. Sample OWB WPU OWP estcrification percent percent DryW lbs.

19a 25 83 20. 7 026 hr. at 135 C. 1. 0 ii 202 207 19b 25 7E) 19. 7 0.5hr. at 135 G 1.1 10 202 205 55 XAMP 20 lated below, show formation of3-( lH,l

Three samples of X 80 cotton print cloth, 20a, 20b and 20c, wereconditioned and weighed as in Example l 1. Two of them (20a and 2017)were padded with a 20 percent solution of ethylenebis(carbonic[bis(trifluo romethyl)methoxy]acetic anhydride), the product ofH,7H,dodecafluoroheptyloxy)propionic esters of cellu- 55 lose.

TABLE 12 Anhydride 01' Exam le Extent 1, percent, in i- Correctedutilization methyliorrnamide weight of padded Tensile Conditions forgain, reagent, strength, Sample OWB WP U OWF csterification percentpercent lbs.

2111 20 104 20. 8 0.25 hr. at 135 C. 8.14 47 21b 20 101 20. 2 0.5 hr. at135 C 8. 13 48 56 10 20 98 19. 6 0.25 hr. at 163 C 7. 87 48 21d 20 4hrs. at 90 C 1.0

1 Not padded; immersed.

19 EXAMPLE 22 Two samples of 80 X 80 cotton print cloth, 22a and 22b,were conditioned and weighed as in Example 1 1. They were padded with a25 percent solution of suberic bis(ethylcarbonic anhydride) indimethylformamide and cured under conditions promoting acylation andcross-linking, in accordance with data tabulated below in Table 13.After the esterification reaction, each sample was rinsed, conditionedand weighed as in Example 1 1. All of the suberoyl part of the carboniccarboxylic anhydride padded on both samples acylated the cellulose,i.e., there was 100 percent utilization of the reagent padded on thefabric, based on weight gains. Results tabulated below show that creaserecovery angles were increased markedly above the control values of 193C. (dry) and 162C. (wet).

EXAMPLE 24 Two samples of 80 X 80 cotton print cloth, 24a and 24b, wereconditioned and weighed as in Example 11. They were padded with a 25percent solution of sebacic bis(ethylcarbonic anhydride) indimethylformamide and cured (heat treated) at 135 C. for various timesas tabulated below in Table 15. After the reaction, which took placeunder conditions promoting acylation and cross-linking, each sample wasrinsed, conditioned and weighed as in Example 11. Practically all of thesebacoyl part of the carbonic carboxylic anhydride padded on bothsamples acylated the cellulose, i.e., there was 97-98 percentutilization of the reagent padded on the fabric, based on weight gains.Results tabulated below show high crease recovery angles, even at a hightensile strength relative to the control specimens.

TAB IJE 13 Suberic bis-(ethylcarbonic anhydride), Extent percent, indimethyl- Corrected utilization Crease recovl'ormamide weight of paddedery, degrees Tensile Conditions for gain, reagent, strength Sample OWBWPU OWF esterifieation percent percent Dry Wet lbs.

22a 25 91 22. 7 0.25 hr. at 135 C 13.5 100 281 260 36 22b 25 86 21.5 0.5hr. at 135 C 12.3 100 288 268 40 i TABLE 15 Sebacic bis(ethylcarbonicanhydride), Extent percent, in dimethyl- Corrected utilization Creaserecovl'orrnamide weight of padded ery, degrees Tensile Conditions forgain, reagent, strength, Sample OWB WPU OWF esteriiication percentpercent Dry W lbs.

25 19. 7 0.25 hr. at 135 C. l. 18 97 284 255 38 25 74 18.5 0.5 hr. at135 C. 8.72 08 280 252 57 Untreated 193 162 5!) 1 Average results on 5specimens.

EXAMPLE 23 EXAMPLE 25 Four samples of X 80 cotton print cloth, 23a, 23b,23c and 23d, were conditioned and weighed as in Example ll. Two of them(230 and 23b) were kept wet with a 25 percent solution of adipicbis(ethylcarbonic anhydride) in a sealed test tube for various times andtemperatures as shown in Table 14 below. The remaining two samples, 230and 23d, were padded with the 25 percent solution and then were heattreated for the times and temperatures indicated in Table 14. After thereaction period, wherein each sample was subjected to conditions forformation of adipic esters of cellulose, and subsequent cross-linking,each sample was rinsed, conditioned and weighed as in Example 1 1. Theresults tabulated below in Table 14 show that good crease recoveryangles resulted by the use of this carbonic carboxylic anhydride whichprovides adipoyl radicals capable of cross-linking the cellulose.

The results below also show that although the acylation proceeds fairlyrapidly at higher temperatures, it may also be accomplished at muchreduced temperatures for longer periods of time.

Single-ply cotton yarn was selected of such a size that a 15,540 yardlength of it weighed a pound. It was purifled by extraction with ethanoland by scouring with an aqueous solution of sodium hydroxide (2%), andit was dried for 16 hours at 50 C. in vacuo (under 1 torr). Accuratelyweighed samples, each approximately 4.7 grams, were kept for 20 hours indimethylformamide (5 ml. per gram of cotton) in order to pre-swell them.Then benzoic ethylcarbonic anhydride (1 to 4 grams per gram of cotton)was added to each of three samples (25a, 25b, 250) in the amounts setforth in Table 16 below. The benzoylation of the cellulose was carriedout at 114 1 4 C. for 1.25 i 0.25 hours. The treated yarn was washedwith methanol, and ovendried. The degree of substitution of cellulosichydroxyl by benzoyl, i.e., the degree of esterification or benzoylation,was calculated from the weight gain on a bone-dry basis. Results aregiven in Table 16.

TABLE 14 Adipic bis(et11ylcarbonic anhydride) Extant percent, indimethyl- Corrected utilization Crease recoviormamide weight 01 paddedery, degress Conditions ior gain, reagent, esterification percentpercent Dry Wet 24 hrs. at 22 C 0.4 5 4 hrs. at 00 C 1.4 17 0.25 hr. atC. 6.3 66 246 228 0.5 hr. at 135 C. 5. 5 62 248 222 TABLE 16 Grams ofbenzoic Extent ethylcarbonic Weight Degree of utilization anhydride per.gain, substitution of reagent,

Sample gram of cotton percent by benzoyl percent 25a 1 9. 3 0. 144 17. 325b 2 12. 0. 186 10. 8 250 4 l2. 8 0. 200 6. 0

Variations were carried out which showed that the degree of substitutionby benzoyl was not substantially affected by (a) varying thedimethylformamide-to-cotton ratio (from 3 to 12 ml. of dimethylformamideper gram of cotton), (b) pre-swelling time, or (c) increasing thereaction temperature to 150 C.

Products having degrees of substitution in excess of 0.2 were preparedby successive benzoylations by means of benzoic ethylcarbonic anhydridefollowing removal of by-products at each stage. A sample given 8successive benzoylations had a final degree of substitution of 0.99.

EXAMPLE 26 A sample of 80 X 80 cotton print cloth was conditioned andweighed as in Example 11. it was padded with a 20% solution ofethylcarbonic (polystyrene) carboxylic anhydride (the product of Example8) in dimethylformamide so the wet pick-up was 91 percent. The samplewas dried at 50 C., then cured for 0.25 hour at 135 C. Next it wasrinsed in toluene, in dimethylformamide, and finally in a 0.1 percentaqueous solution of the nonionic detergent used in Example 1 1. Despitethe action of the strong solvents and detergent, a permanent weight gainof 1.12 percent persisted, indicating that esterification had occurred.

EXAMPLE 27 Six samples of 80 X 80 cotton print cloth (27a-27f) wereconditioned and weighed as in Example 1 1. They were padded with orpercent solutions of ethylcarbonicl1-[fluorobis(trifluoro-methyl)methoxylundecanoic anhydride (C H EO theproduct of Example 9) in dimethylformamide, dried at approximately 38C., and cured at various times and temperatures in accordance with datatabulated below in Table 17, to form 1 l-[fluorobis(trifluoromethyl)methoxy]undecanoic esters of cellulose. After theesterification reaction, each sample was rinsed in dimethylformamide andin water.

Results of measurements of the several samples are tabulated below inTable 17.

Examination of sample 27a showed it had a boundfluorine content of 2.98percent. Sample of 27a was thereafter exposed to 0.5 normal sodiumhydroxide for 3 hours at room temperature, with the result that a 22EXAMPLE 28 A sample of 80 X 80 cotton print cloth was conditioned andweighed as in Example 11. 1t was padded with a 20 percent solution ofethylenebis[carbonic 4- [fluorobis(trifluorornethyl)methoxyl-butyricanhydride] (C H F O the product of Example 10) in dimethylformamide sothe wet pick-up was 94 percent. The sample was cured for 0.25 hour atapproximately 163 C. Next it was rinsed in dimethylformamide, then in a0.1 percent aqueous solution of the nonionic detergent used in Example11. When dry, the weight gain was found to be 2.5 percent, indicatingthat the efficiency in the utilization of the anhydride reagent in theformation of esterified cellulose had been 17 percent. Thebound-fluorine content of the fabric sample was 1.31 percent.

From the above description and representative examples of the presentinvention, it is seen that the carbonic carboxylic anhydrides esterifyhigh molecular weight polyols, such as cellulose, effectively undermild, practically neutral, conditions. No catalysts are needed, andheating is minimal compared with prior practices for esterifyingcellulose and the like. The process does not involve fixed acids orstrong acids, and such acids are neither needed nor produced.Consequently, undesirable side effects are greatly minimized, notablydepolymerization, degradation, and hydrolyt'ic cleavage. Accordingly,the present process permits the ready preparation of valuable esters ofcellulose yet avoids much of the damage to the substrate formerlyconnected with the modification of hydroxylated polymers byesterification.

It is understood that the above description of my invention isexemplary, and that modifications could readily be suggested by thoseskilled in the art to the specific processes described without departingfrom the spirit of the invention.

What 1 claim is:

1. A compound having the formula:

wherein y is an integer of from 1 to 12 and R" is a lower alkaline grouphaving from one to 12 carbon atoms.

2. A compound having the formula:

a )z l30( zhrfiofiOCzHs weight loss of 1.94 percent occurred. The lossof reagent was 29 percent from alkaline hydrolysis, and the resultingfabric sample was found to have a fluorine content of 2.00 percent.

TABLE 17 Anhydride reagent (C17 25 7 5 percent from, Weight Extentdimethyllormamide gain utilization Tensile Conditions for found, ofreagent, strength, Sample OWB WPU OWF osterification percent percentlbs.

27;), l 20 {)4 l8. 8 0.25 111'. at 136 C. 7. 12 48 53 271) 20 .14 18. 87. 68 51 52 27c 20 I4 18. 8 7. (i4 51 52 27d. 10 ill 9.1 4. 30 Eli 55271... 10 J1 SL1 4. 46 (i2 52 271' a 10 J1 11 4. 76 66 54

2. A compound having the formula: